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1. 发明申请

WO2014111446A1 PROCESS FOR THE PREPARATION OF FORMYLVALERIC ACID AND ADIPIC ACID 审中-公开
标题翻译：制备异戊酸和丙二酸的方法
公开(公告)号：WO2014111446A1
公开(公告)日：2014-07-24
申请号：PCT/EP2014/050764
申请日：2014-01-16
申请人： DSM IP ASSETS B.V.
发明人： PARTON, Rudy Francois Maria Jozef , JANSSEN, Michèle Catherine Christianne , ENGENDAHL, Barthel , VRIES, DE, Johannes Gerardus
IPC分类号： C07C51/14 , C07C51/373 , C07C51/42 , C07C51/44 , C07C51/48 , C07C57/03 , C07C59/147 , C07C51/09 , C07D307/32
CPC分类号： C07C51/373 , C07C51/09 , C07C51/12 , C07C51/14 , C07C51/42 , C07C51/44 , C07C51/48 , C07D307/32 , C07C59/147 , C07C55/14 , C07C57/03
摘要： The invention relates to a process for the production of 5-formylvaleric acid and adipic acid or esters thereof from an isomeric mixture of pentenoic acid or esters thereof said mixture comprising at least 4-pentenoic acid or esters thereof, and further comprising 3-pentenoic acid and/or 2-pentenoic acid or esters thereof, theprocess comprising: (a) subjecting the isomeric mixture of pentenoic acid to a hydroformylation reaction comprising a hydroformylation catalyst which is non-isomerizing towards the pentenoic acid or esters thereof to obtain a mixture comprising 5-formylvaleric acid or esters thereof and further comprising 3-pentenoic acid and/or 2-pentenoic acid, or esters thereof; (b) separating the 3-pentenoic acid and/or 2-pentenoic acid, or esters thereof from the 5-formylvaleric acid or esters thereof; (c) subjecting the separated pentenoic acids or esters thereof to a carbonylation reaction comprising an isomerizing carbonylation catalyst to obtain adipic acid or esters thereof; (d) optionally isolating the adipic acid or ester thereof; and (e) optionally isolating the separated 5-formylvaleric acid or esters thereof. The process allows for efficient production of two different intermediates for producing polyamide using a single process, with good selectivity, little waste, in an economically efficient fashion. The process is very suitable to use an isomeric pentenoic acid mixture obtained from valerolactone, and can be used to produce renewable polyamide intermediates using a single process.
摘要翻译：本发明涉及一种由戊烯酸或其酯的异构体混合物生产5-甲酰戊酸和己二酸或其酯的方法，所述混合物包含至少4-戊烯酸或其酯，并且还包含3-戊烯酸和/或2-戊烯酸或其酯，所述方法包括：（a）使戊烯酸的异构体混合物进行加氢甲酰基化反应，所述加氢甲酰化反应包含对戊烯酸或其酯异构化的加氢甲酰化催化剂，以获得包含5 - 甲酰基戊酸或其酯，并且还包含3-戊烯酸和/或2-戊烯酸或其酯; （b）从5-甲酰戊酸或其酯分离3-戊烯酸和/或2-戊烯酸或其酯; （c）使分离的戊烯酸或其酯进行包含异构化羰基化催化剂的羰基化反应以获得己二酸或其酯; （d）任选分离己二酸或其酯; 和（e）任选分离分离的5-甲酰基戊酸或其酯。该方法允许以经济有效的方式有效地生产用于使用单一工艺生产聚酰胺的两种不同中间体，具有良好的选择性，少量的废料。该方法非常适合于使用由戊内酯获得的异戊烯酸混合物，并可用于使用单一工艺生产可再生聚酰胺中间体。

2. 发明申请

WO2012131028A1 PROCESS TO PRODUCE ADIPIC ACID AND DIESTERS THEREOF IN A CARBONYLATION PROCESS USING PALLADIUM BIDENTATE BIPHOSPHATE LIGANDS 审中-公开
标题翻译：使用双磷酸双磷酸酯配位体在碳化工艺中生产其酸和其它物质的方法
公开(公告)号：WO2012131028A1
公开(公告)日：2012-10-04
申请号：PCT/EP2012/055769
申请日：2012-03-30
申请人： DSM IP ASSETS B.V. , VRIES, DE, Johannes Gerardus , SEREINIG, Natascha , VAN DE VONDERVOORT, Elisabeth Wilhelmina Maria , JANSSEN, Michèle Catherine Christianne
发明人： VRIES, DE, Johannes Gerardus , SEREINIG, Natascha , VAN DE VONDERVOORT, Elisabeth Wilhelmina Maria , JANSSEN, Michèle Catherine Christianne
IPC分类号： C07C67/38 , C07C67/03 , C07C69/44 , C07C69/533 , C07C51/09 , C07C55/14 , C07C209/48 , C07C211/12 , C07C253/00 , C07D307/33
CPC分类号： C07C253/00 , C07C51/09 , C07C51/14 , C07C51/31 , C07C51/412 , C07C67/03 , C07C67/38 , C07C209/48 , C07C211/12 , C07C255/04 , C07C69/44 , C07C69/533 , C07C63/313 , C07C55/14
摘要： The invention relates to a carbonylation process for the preparation of a compound of formula (I) XOOC-(CH 2 ) 4 -COOY (I) wherein X and Y can independently represent H and/or alkyl, said carbonylation process comprising reacting: (a) a composition comprising at least one isomeric methyl pentenoate; (b) a source of Pd; (c) a bidentate di-phosphine of formula II, R 1 R 2 P - R 3 - R - R 4 - PR 5 R 6 (II) wherein P represents a phosphorus atom; R 1 , R 2 , R 5 and R 6 can independently represent the same or different optionally substituted organic groups containing a tertiary carbon atom through which the group is linked to the phosphorus atom; R 3 and R 4 independently represent optionally substituted lower alkylene groups and R represents an optionally substituted aromatic group; (d) a source of anions derived from an acid with a pKa etceteras instead of using fossil sources.
摘要翻译：本发明涉及用于制备式（I）化合物XOOC-（CH 2）4 -COOH（I）的羰基化方法，其中X和Y可以独立地表示H和/或烷基，所述羰基化方法包括使（a ）包含至少一种异构戊烯酸戊酯的组合物; （b）Pd源; （c）式II的二齿二膦，R1R2P-R3-R-R4-PR5R6（Ⅱ），其中P表示磷原子; R1，R2，R5和R6可以独立地表示相同或不同的含有叔碳原子的任选取代的有机基团，该基团通过该有机基团与磷原子连接; R3和R4独立地表示任选取代的低级亚烷基，R表示任选取代的芳族基团; （d）源自pKa <3的酸的阴离子源; （e）一氧化碳; 和（f）包含化合物的OH基团，其中产生（I）的条件，其特征在于至少一种异构戊烯酸异戊酯包括2-戊烯酸甲酯。该方法有利地具有高转化率，并且可以使用而不需要从也含有3-和/或4-戊烯酸甲酯的混合物中分离2-戊烯酸甲酯以使2-戊烯酸甲酯异构化。该方法适用于生产己二酸二甲酯，己二酸和六亚甲基二胺及其衍生产物，如可再生能源如尼龙6,6，而不是使用化石源。

3. 发明申请

WO2013107904A1 PROCESS TO PRODUCE ALKANOIC ACID ESTERS IN A CARBONYLATION PROCESS USING LEWIS ACIDS AS ACID PROMOTOR 审中-公开
标题翻译：使用柠檬酸作为酸性引发剂在羰化过程中生产酸性酯的方法
公开(公告)号：WO2013107904A1
公开(公告)日：2013-07-25
申请号：PCT/EP2013/051038
申请日：2013-01-21
申请人： DSM IP ASSETS B.V.
发明人： JANSSEN, Michèle Catherine Christianne , VRIES, DE, Johannes Gerardus
IPC分类号： C07C67/38 , C07C67/03 , C07C51/09 , C07C209/48 , C07C211/12 , C07C253/00 , C07D307/33 , C07C69/44 , C07C69/533 , C07C55/14
CPC分类号： C07C67/38 , C07C69/44
摘要： The invention relates to an alkoxycarbonylation process for the preparation of an optionally substituted alkanoic acid ester comprising reacting: (a) an optionally substituted alkene or a mixture thereof; (b) a source of a group 8-10 metal; (c) a phosphorous ligand having a pKa of greater than 3; (d) a Lewis acid having a water exchange rate constant of substantially 10 7 s -1 and a hydrolysis constant of between 4 and 10 M, or a mixture thereof; (e) carbon monoxide; and (f) an alkanol, under conditions wherein an alkanoic acid ester is produced. Said process advantageously allows for good TOF and/or selectivity and may avoid the inactivation of the catalytic metal.
摘要翻译：本发明涉及用于制备任选取代的链烷酸酯的烷氧基羰基化方法，包括使（a）任选取代的烯烃或其混合物反应; （b）8-10组金属的来源; （c）pKa大于3的磷配位体; （d）水交换率常数为107s-1，水解常数为4〜10M的路易斯酸或其混合物; （e）一氧化碳; 和（f）链烷醇，其中产生链烷酸酯的条件。所述方法有利地允许良好的TOF和/或选择性，并且可以避免催化金属的失活。

4. 发明申请

WO2009150173A1 USE OF DISSOLVED IRON NANOPARTICLES AS CATALYST IN ADDITION REACTIONS 审中-公开
标题翻译：使用溶解铁纳米粒子作为添加剂反应中的催化剂
公开(公告)号：WO2009150173A1
公开(公告)日：2009-12-17
申请号：PCT/EP2009/057168
申请日：2009-06-10
申请人： DSM IP Assets B.V. , VRIES, DE, Johannes Gerardus , LEFORT, Laurent , PHUA, Pim Huat
发明人： VRIES, DE, Johannes Gerardus , LEFORT, Laurent , PHUA, Pim Huat
IPC分类号： B01J23/745 , B01J35/00 , C07C5/02 , C07C29/132 , C07C209/00 , C07F5/02 , C07F7/08
CPC分类号： B01J23/745 , B01J20/28007 , B01J35/0013 , B82Y30/00 , C07B35/02 , C07C5/03 , C07C5/08 , C07C5/09 , C07C29/17 , C07C45/62 , C07C2523/745 , C07C2601/14 , C07C2602/42 , C07C49/04 , C07C33/025 , C07C31/125
摘要： Comprising dissolved iron (0) nanoparticles, obtained by reducing an iron salt in the presence of a stabilizer and a reductant in an organic solvent and substantially in the absence of water. The present invention further relates to a process for the addition of HX (hydrogenation) to an unsaturated compound using a catalyst.
摘要翻译：包括溶解的铁（0）纳米颗粒，其通过在稳定剂和还原剂存在下在有机溶剂中并基本上不存在水而还原铁盐而获得。本发明还涉及使用催化剂向不饱和化合物中加入HX（氢化）的方法。

5. 发明申请

WO2014009521A1 PROCESS FOR THE PRODUCTION OF FURFURAL AND LEVULINIC ACID FROM LIGNOCELLULOSIC BIOMASS 审中-公开
标题翻译：从肉桂生物量生产糠酸和橄榄酸的方法
公开(公告)号：WO2014009521A1
公开(公告)日：2014-01-16
申请号：PCT/EP2013/064782
申请日：2013-07-12
申请人： DSM IP ASSETS B.V.
发明人： VRIES, DE, Johannes Gerardus , KROON, Johannes Augustinus , PARTON, Rudy Francois Maria Jozef , WOESTENBORGHS, Pierre Louis , RIJKE, DE, Arie
IPC分类号： C07D307/50 , C07C51/00
CPC分类号： C07C51/00 , C07C51/47 , C07D307/50 , C07C59/185
摘要： The invention relates to a process for producing furfural and levulinic acid from lignocellulose-comprising biomass, said process comprising: (a) adding water and optionally an acid to said biomass to form a slurried biomass; (b) subjecting said slurried biomass to hydrolysis to form a hydrolysate comprising C5 and C6 sugars and further comprising (insoluble) cellulose and lignin; (c) subjecting said hydrolysate comprising said C5 and C6 sugars and said (insoluble) cellulose and lignin to solid / liquid separation to yield a first aqueous fraction comprising at least part of said C5 and C6 sugars and a first solid fraction comprising at least part of said cellulose and lignin; (d) optionally concentrating said first aqueous fraction; (e) adding an organic solvent to the (optionally concentrated) first aqueous fraction to form a biphasic system; (f) heating said biphasic system to a temperature within the range of 120 - 220°C and maintaining said biphasic system at that temperature range for a time sufficient to form furfural; (g) cooling the biphasic system comprising furfural obtained in step (f); (h) optionally subjecting the cooled biphasic system obtained in step (g) to solid / liquid separation and recovering the biphasic system; (i) subjecting the cooled biphasic system obtained in step (g) or the recovered biphasic system obtained in step (h) to a separation step to yield an organic phase comprising at least part of said furfural and an aqueous phase comprising at least part of said C6 sugars and optionally further comprising furfural; (j) optionally recovering furfural from said organic phase; (k) optionally using the recovered organic phase obtained in step (j) to extract furfural from the aqueous phase obtained in step (i) by adding said recovered organic phase to said aqueous phase and repeating step (i) and optionally step (j); (I) adding water and optionally an acid to the first solid fraction obtained in step (c) to form a suspension; (m) subjecting the suspension obtained in step (I) to a temperature of between 140 and 220°C to form levulinic acid; (n) subjecting the suspension comprising levulinic acid obtained in step (m) to solid / liquid separation to yield a second aqueous fraction comprising levulinic acid and a solid fraction; and (o) optionally recovering said levulinic acid from the second aqueous fraction. The process advantageously allows for the production of both furfural and levulinic acid from lignocellulosic biomass, with no or little waste. Solvents and energy are used in an efficient way. The process can be done in a continuous fashion and gives less reactor fouling and results in less insoluble char. It benefits energy conservation.
摘要翻译：本发明涉及由含木素纤维素的生物质生产糠醛和乙酰丙酸的方法，所述方法包括：（a）向所述生物质中加入水和任选的酸以形成浆状生物质; （b）使所述浆状生物质水解以形成包含C5和C6糖的水解产物，并进一步包含（不溶性）纤维素和木质素; （c）使包含所述C5和C6糖的所述水解产物和所述（不溶性）纤维素和木质素进行固/液分离，得到包含至少部分所述C5和C6糖的第一含水部分和包含至少部分的第一固体部分的所述纤维素和木质素; （d）任选地浓缩所述第一含水部分; （e）向（任选浓缩的）第一含水部分中加入有机溶剂以形成双相体系; （f）将所述两相系统加热至120-220℃的温度，并将所述两相体系在该温度范围内维持足以形成糠醛的时间; （g）冷却包含在步骤（f）中获得的糠醛的双相系统; （h）任选地将步骤（g）中获得的冷却的双相体系进行固/液分离并回收双相体系; （i）将步骤（g）中获得的冷却的双相系统或步骤（h）中获得的回收的双相体系进行分离步骤，得到包含至少部分所述糠醛的有机相和含有至少部分所述C6糖并且任选地进一步包含糠醛; （j）任选地从所述有机相中回收糠醛; （k）任选地使用步骤（j）中获得的回收的有机相通过将所述回收的有机相加入到所述水相中并重复步骤（i）和任选的步骤（j）从步骤（i）获得的水相中提取糠醛， ; （I）向步骤（c）中获得的第一固体部分加入水和任选的酸以形成悬浮液; （m）使步骤（I）中获得的悬浮液温度在140-220℃之间以形成乙酰丙酸; （n）使包含步骤（m）中获得的乙酰丙酸的悬浮液进行固/液分离以产生包含乙酰丙酸和固体级分的第二含水级分; 和（o）任选地从第二含水部分回收所述乙酰丙酸。该方法有利地允许从木质纤维素生物质生产糠醛和乙酰丙酸，没有或少量的浪费。溶剂和能量以有效的方式使用。该方法可以以连续的方式进行，并且产生更少的反应器结垢并导致较不溶性的焦炭。它有利于节能。

6. 发明申请

WO2013107902A1 PROCESS FOR THE SEPARATION OF A DISSOLVED CATALYST SYSTEM FROM AN ALKOXYCARBONYLATION REACTION MIXTURE 审中-公开
标题翻译：从烷基羧化反应混合物中分离溶解的催化剂体系的方法
公开(公告)号：WO2013107902A1
公开(公告)日：2013-07-25
申请号：PCT/EP2013/051020
申请日：2013-01-21
申请人： DSM IP ASSETS B.V.
发明人： VRIES, DE, Johannes Gerardus , JANSSEN, Michèle Catherine Christianne , PARTON, Rudy Francois Maria Jozef , HOVING, Hendrik Derk
IPC分类号： C07C67/38 , B01J31/40 , B01D61/02 , B01J31/24
CPC分类号： B01J31/4038 , B01D61/022 , B01D61/025 , B01D61/027 , B01D61/145 , B01D61/58 , B01J31/24 , B01J31/4053 , B01J31/4061 , B01J2231/321 , B01J2531/824 , C07C67/38 , C07C67/56 , Y02P20/584 , C07C69/44
摘要： The invention relates to a to separate a dissolved catalyst system from a mixture obtained by an alkoxycarbonylation reaction, the process comprising subjecting said mixture to membrane filtration using a membrane which is impermeable to molecules having a molecular weight of 1 kDa or more to yield a retentate and a permeate, wherein the concentration of the dissolved catalyst system in the retentate is higher than in the permeate. Said process may advantageously reduce inactivation of the catalyst system.
摘要翻译：本发明涉及一种从通过烷氧基羰基化反应获得的混合物中分离出溶解的催化剂体系，该方法包括使用对分子量为1kDa或更大的分子不可渗透的膜对所述混合物进行膜过滤以产生滞留物和渗透物，其中所述渗余物中溶解的催化剂体系的浓度高于渗透物中的浓度。所述方法可有利地减少催化剂体系的失活。

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